JP2006057091A - Fire-resisting coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fire-resisting coating capable of forming a heat insulating layer, based on substances each changed into a foam layer and carbonized, in case of a fire, and a film-forming binder, a blowing agent, a commonly-used auxiliary agent, and an additive. <P>SOLUTION: This fire-resisting coating forms the heat insulating layer, wherein the fire-resisting coating contains a flame retardant mixture containing a phosphorus-based/nitrogen-based flame retardant, and a phosphinic acid salt expressed by general formula (I) (R<SP>1</SP>and R<SP>2</SP>are identical to or different from each other and are each a 1-6C linear or branched alkyl or an aryl; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K or a protonated nitrogen base; and m is 1 to 4) and/or a diphosphinic acid salt expressed by general formula (II) (R<SP>3</SP>is a 1-10C linear or branched alkylene, a 6-10C arylene, a 6-10C alkylarylene or a 6-10C arylalkylenene; n is 1 to 4; and x is 1 to 4) and/or a polymer thereof. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is described in German Patent Application No. 102004039758.9, filed on August 17, 2004, which is the basis of the priority of the present application, the contents of which are all described herein.

  The present invention relates to a fire-resistant paint for forming a heat-insulating layer based on foamed layers and carbonized materials in the event of a fire, and film-forming binders, blowing agents, conventional auxiliaries and additives.

  The fire-resistant paint (also called foaming paint) that forms a thermal insulation layer foams when exposed to temperatures that occur in the event of a fire, and the above-mentioned fire-resistant paint foams in this way, resulting in steel Prevent or at least suppress heat transfer to workpieces, ceilings, walls, cables, pipes, etc.

  U.S. Pat. No. 4,965,296 discloses a flame retardant material comprising a flame retardant coating and an electrically conductive material. The flame retardant coating material is composed of each substance that generates bubbles and carbonizes, a compound that generates gas, a film-forming binder, and a suitable solvent. Other conventional ingredients may be present if desired.

  U.S. Pat. No. 4,879,320 describes a similar flame retardant composition in which a ceramic fiber material is added instead of a conductive material.

  U.S. Pat. No. 6,096,812 discloses a foamable paint based on an epoxy resin and having a dry film with a particularly low intrinsic density.

  These paints are primarily used to protect ships, oil platforms and other equipment for storage and in the processing of flammable hydrocarbons. These devices generally require a large amount of fire protection material to ensure proper insulation of the metal components. This inevitably significantly increases the load weight on the structure to be protected. However, the additional weight loaded on weight loaded and unloaded metal structures is often limited (eg, oilfield platforms).

  The purpose of the above prior art fire protection paints is to achieve maximum fire protection time with minimum application.

  One solution to achieve low coating weight can be achieved by reducing the inherent density of the dried coating (US Pat. No. 6,096,812). The disadvantage is that the fire performance often decreases incidentally.

  The overall disadvantage of the above fire protection paint is that the foam structure that occurs in the case of a fire does not achieve an improvement in thermal insulation and the reaction does not start until the temperature T reaches 180 ° C. or higher.

  In fact, in many cases, the reaction will not begin unless a temperature much higher than this range is reached.

  Therefore, one of the objects of the invention described below provides a fire protection paint that achieves a longer fire protection time with the same usage, or a fire protection time comparable to the prior art with a smaller application amount. That is.

  This task is also achieved by starting the reaction at a temperature T of <180 ° C. (less than 180 ° C.).

  Accordingly, the present invention provides a fireproof paint for forming a heat insulating layer, a phosphorus-based / nitrogen-based flame retardant and a phosphinate represented by the following formula (I) and / or a diphosphinate of the following formula (II) and / or these: A fire retardant paint comprising a flame retardant mixture comprising a polymer of:

[Where:
R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ alkyl and / or aryl;
R ³ represents linear or branched C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, C ₆ -C _10-
Alkylarylene, or C ₆ -C ₁₀ -arylalkylene,
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;
m is 1 to 4,
n is 1 to 4,
x is 1-4].

The phosphorus-based / nitrogen-based flame retardant is a nitrogen-containing phosphate represented by the formula (NH ₄ ) _y H _3-y PO ₄ or (NH ₄ PO ₃ ) _z , where y is 1 to 3. It is advantageous that z is 1 to 10,000.

  The phosphorus / nitrogen flame retardant is particularly advantageously ammonium hydrogen phosphate, ammonium dihydrogen phosphate and / or ammonium polyphosphate.

The phosphorus-based / nitrogen-based flame retardant is preferably an ammonium polyphosphate represented by the formula (NH ₄ PO ₃ ) _n , wherein n is 10 to ≦ 1000, preferably 200 to ≦ 1000.

  The phosphorus / nitrogen flame retardant is a reaction product of melamine and phosphoric acid or condensed phosphoric acid, or a reaction product of melamine condensation product and phosphoric acid or condensed phosphoric acid or products thereof It is a mixture of

  The phosphorus / nitrogen flame retardant is particularly preferably melam, melem or melon, dimelamine phosphate, dimelamine pyrophosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate Phosphate and / or melem polyphosphate, or mixed polysalts of these types.

  The fire-resistant paint of the present invention for forming a heat insulating layer is 0.1 to 100 (phosphorus / nitrogen flame retardant): 100 to 0.1 (phosphinic acid salt), preferably phosphorus / nitrogen flame retardant. It is preferred to contain phosphinates of the formula (I) and / or diphosphinates of the formula (II) and / or contain these polymers.

  The fire retardant coating of the present invention that forms a thermal insulation layer contains a phosphorus / nitrogen flame retardant in a weight ratio of 1-50 (phosphorus / nitrogen flame retardant): 50-1 (phosphinic acid salt) and has the formula Containing phosphinates of (I) and / or containing diphosphinates of formula (II) and / or containing these polymers.

The fire protection coating of the present invention forming the heat-insulating layer preferably comprises A) 1 to 99% by weight of epoxy resin and B) 1 to 99% by weight of phosphorus / nitrogen flame retardant and phosphinic acid salt of formula (I) And / or flame retardant mixtures containing diphosphinic acid salts of the formula (II) and / or polymers thereof,
C) Contains 0-60% by weight of other additives.

The fire-resistant paint of the present invention which forms the heat-insulating layer is particularly preferably A) 10 to 90% by weight of epoxy resin and B) 2 to 60% by weight of phosphorus / nitrogen flame retardant and phosphinic acid of formula (I) Flame retardant mixtures containing salts and / or diphosphinic salts of the formula (II) and / or polymers thereof,
C) Contains 3 to 45% by weight of other additives.

The fire-resistant paint of the present invention forming the heat-insulating layer is particularly preferably A) 30 to 85% by weight of an epoxy resin and B) 3 to 50% by weight of a phosphorus / nitrogen flame retardant and a phosphine of the formula (I) Flame retardant mixtures containing acid salts and / or diphosphinic acid salts of the formula (II) and / or polymers thereof,
C) 5-40% by weight of other additives.

  The fire-resistant paint of the present invention for forming a heat-insulating layer is particularly preferably 0 to 60% by weight of additives such as accelerators, fillers, auxiliaries, swelling agents, nitrogenous synergists, carbon donating substances, pigments, plasticizers, And / or reactive diluents and optionally other additives. The total amount of all these components is always 100% by weight.

  M is preferably calcium, aluminum or zinc.

R ¹ and R ² are the same or different and are linear or branched and are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.

R ³ represents methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene; phenylene or naphthylene; methylphenylene, ethylphenylene, tert-butyl. Preference is given to phenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene; phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.

The protonated nitrogen base is preferably a protonated base of ammonia, melamine or triethanolamine, particularly preferably NH ₄ ⁺ .

R ¹ and R ² are the same or different from one another and are preferably linear or branched C ₁ -C ₆ -alkyl and / or phenyl.

In particular, R ¹ and R ² are the same or different from each other and are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.

The halogen-free epoxy compounds (hereinafter also referred to as polyepoxy compounds) used according to the present invention may be saturated or unsaturated compounds, and may be aliphatic, alicyclic, aromatic and / or heterocyclic compounds. In addition, they may contain substituents that do not cause any problem side reactions under mixing or reaction conditions, such as alkyl substituents, aryl substituents, ether groups or the like. . Mixtures of various polyepoxy compounds can also be used. The number average molecular weight M _n of these polyepoxy compounds may be up to about 9000, but is generally about 150-4000.

  Examples of these polyepoxy compounds include polyhydric, preferably dihydric alcohols, phenols, hydrogenated products and / or novolacs of these phenols (monovalent or polyvalent in the presence of an acidic catalyst). Polyhydric phenols, such as the reaction product of phenol and / or cresols with aldehydes, in particular formaldehyde). These are obtained in a known manner, for example by reaction of individual polyols with epichlorohydrin.

  Examples of polyhydric phenols that can be mentioned here are resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), isomer mixture of dihydroxydiphenylmethane (bisphenol F), 4,4 ' -Dihydroxydiphenylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-benzophenone, 1,1-bis (4-hydroxyphenyl) ethane 1,1′-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxy-tert-butylphenyl) propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, tris ( 4-hydroxyphenyl) methane, bi It is (4-hydroxyphenyl) 1,1'-ether.

  Bisphenol A and bisphenol F are preferred.

  Other suitable polyepoxy compounds include polyglycidyl ethers of polyhydric aliphatic alcohols. Examples that may be mentioned of these polyhydric alcohols are 1,4-butanediol, 1,6-hexanediol, polyalkylene glycols, glycerol, trimethylolpropane, 2,2-bis (4-hydroxycyclohexyl) propane and There is pentaerythritol.

  Other polyepoxy compounds that can be used include epichlorohydrin or similar epoxy compounds and aliphatic, cycloaliphatic or aromatic polycarboxylic acids such as oxalic acid, adipic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid , Tetrahydrophthalic acid, or hexahydrophthalic acid, or naphthalene-2,6-dicarboxylic acid, tetrahydrophthalic acid, or hexahydrophthalic acid, or naphthalene-2,6-dicarboxylic acid, or a reaction with a dimerized fatty acid There are (poly) glycidyl esters obtained by: Examples of these are diglycidyl terephthalate and diglycidyl hexahydrophthalate.

  Polyepoxy compounds, such as glycidyl esters of acrylic acid or methacrylic acid, which can be produced by emulsion copolymerization using olefinically unsaturated compounds containing these epoxy groups randomly and containing epoxy groups across the molecular chain It is advantageous in some cases to use.

  Examples of other polyepoxy compounds that can be used are those based on heterocyclic systems such as hydantoin epoxy resins, triglycidyl isocyanurate, and / or oligomers thereof, tolglycidyl-p-aminophenol, triglycidyl-p -Aminodiphenyl ether, tetraglycidyl diaminodiphenyl ester, tetraglycidyl diaminodiphenyl ether, tetrakis (4-glycidoxyphenyl) ethane, urazole epoxides, uracil epoxides, oxazolidinone-modified epoxy resins, and aromatic amines such as Polyepoxides based on aniline, such as N, N-diglycidylaniline, diaminodiphenylmethane and N, N′-dimethylaminodiphenylmethane or N, N′-dimethyla There is Roh diphenyl sulfone. Other suitable polyepoxy compounds are "Handbook of Epoxy Resins" by Henry Lee and Kris Neville, McGraw-Hill Book Company, 1967; Henry Lee "Epoxy Resins" American Chemical Society, 1970; Wagner / Sarx, "Lackkunstharze" [Synthetic Paint Resins], Carl Hanser Verlag (1971), 5th edition, pp. 174-196; “Angew. Makromol. Chemie”, vol. 44 (1975), pp. 151-163; German Patent Application No. 27 57 733 And European Patent Application Publication No. 0 384 939 (the contents of these publications will be described here).

  Preferred polyepoxide resins are bisglycidyl ethers based on bisphenol A, bisphenol F or bisphenol S (reaction products of these bisphenols with epichloro (halo) hydrin) or their oligomers, phenol-formaldehyde and / or cresol- Polyglycidyl ether of formaldehyde-novolak, or diglycidyl esters of phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid and / or hexahydrophthalic acid or trimellitic acid, aromatic amines or heterocyclic nitrogenous bases, For example, N, N-diglycidylaniline, N, N, O-triglycidyl-p-aminophenol, triglycidyl isocyanurate or N, N, N ′, N-tetraglycidyl- N-glycidyl compounds of su- (p-aminophenyl) methane, hydantoin epoxy resins or aracid epoxy resins or polyhydric aliphatic alcohols such as 1,4-butanediol, trimethylolpropane or polyalkylene glycols Of di- or polyglycidyl compounds. Also suitable are oxazolidinone-modified epoxy resins. Compounds of this type are already known (see: “Angew. Makromol. Chem.”, 44 (1975), 151-163 and US Pat. No. 3,334,110). The reaction product of bisphenol A diglycidyl ether and diphenylmethane diisocyanate (in the presence of a suitable accelerator) can also be mentioned as an example.

  The polyepoxy resins may be present individually or as a mixture during the production of the fire protection paint of the present invention. Curing agent components that can be used are aliphatic and aromatic polyamines. Aromatic polyamines are described, for example, in EP-A-0,274,646. These are prepared by trimerization of 2,6- or 2,4-diisocyanate alkylbenzenes and then by hydrolysis of the remaining isocyanate groups. These hardener components can be used individually or in a mixed state. These mixtures are commercially available and allow the hardener component to be produced at a low cost.

  Heterocyclic polyamines having urea groups can be used as additional additive hardener components (ie in addition to the actual hardener). The curing agent mixture may also use other aromatic polyamines not more than 30%, such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and / or other heterocyclic polyamines. .

  Advantageous additives present in the fire protection paints of the present invention include accelerators, fillers, auxiliaries, swelling agents, nitrogen-based synergists, carbon donor materials, pigments, plasticizers, and / or reactive diluents.

  Accelerators that can be used are in particular imidazole derivatives such as 2-methylimidazole 2-phenylimidazole, and 2-heptadecylimidazole; phosphines, tertiary amines such as benzylmethylamine and tris (dimethylaminomethyl) phenol, and metals There are soaps and acetylacetonates.

  Examples of fillers and auxiliaries include expandable graphite, boric acid, phosphate esters, quartz, china clay, chalk, wollastonite, talc, antimony trioxide, glass fiber, mineral fiber, aluminum oxide, aluminum hydroxide, water There are magnesium oxide, precipitated silicic acid, silicate and / or powdered cellulose.

  Swelling agents and nitrogenous synergists include melamine and / or guanidine and their salts and / or dicyandiamides. Melamine salts include the melamine phosphate, melamine polyphosphate, melamine cyanurate, melamine borate, and melamine silicate, and the guanidine salt is preferably guanidine phosphate.

As described above, the fire-proof paint of the present invention that forms the heat insulating layer may contain 0 to 60% by weight of an additive. Within the range of 0 to 60% by weight, the following additives may be distributed:
Accelerator: 0 to 25% by weight,
Fillers and auxiliaries: 0 to 100% by weight,
Swelling agent and nitrogen-based synergist: 0 to 100% by weight,
Carbon donor: 0 to 100% by weight,
Pigment: 0 to 50% by weight
Plasticizer: 0 to 50% by weight,
Reactive diluent: 0 to 25% by weight.

  Therefore, the percentage display of each additive is based on the above 0 to 60% by weight as a total amount.

  According to the invention, other advantageous synergists are preferably those of the formulas (III) to (VII)

[Wherein R ^{5 to} R ⁷ are hydrogen atoms; C ₁ -C ₈ -alkyl, C ₅ -C ₁₆ -cycloalkyl substituted or unsubstituted with a hydroxyl group or a C ₁ -C ₄ -hydroxyalkyl group or - alkylcycloalkyl; _C 2 -C ₈ - _alkenyl, C 1 -C ₈ - alkoxy, - acyl, or - _acyloxy, C 6 _{-C 12} - aryl or - arylalkyl, -OR ⁸ and -N (R ⁸ ) R ⁹ , as well as N-alicyclic or N-aromatic systems,
R ⁸ is a hydrogen atom; a C ₁ -C ₈ -alkyl, C ₅ -C ₁₆ -cycloalkyl or -alkyl cycloalkyl substituted or unsubstituted with a hydroxyl group or a C ₁ -C ₄ -hydroxyalkyl group; C ₂ -C ₈ - _alkenyl, C 1 -C ₈ - alkoxy, - acyl or - acyloxy; or _C 6 _{-C 12} - aryl or - arylalkyl,
R ^{9 to} R ¹³ are groups defined for R ⁸ or —O—R ⁸ ;
m and n are 1, 2, 3 or 4 independently of each other;
X is an acid capable of forming an adduct with the triazine compound (III). ]
Or mixtures thereof are preferred.

  Advantageously, the nitrogen-containing synergist is benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, urea cyanurate, dicyandiamide, guanidine.

  Advantageously, the nitrogenous synergist is a condensate of melamine. Examples of condensates of melamine are melem, melam or melon, or higher compounds of this kind, or mixtures thereof and in one example by the method described in WO 96/16948. What can be produced is advantageous.

  The fire protection coating that forms the thermal insulation layer preferably contains carbohydrates as carbonizing substances.

  The carbohydrates used advantageously are pentaerythritol, dipentaerythritol, tripentaerythritol and / or a polycondensate of pentaerythritol.

  Pigments that can be used include carbon black, phthalocyanine pigments, and metal oxides. Titanium dioxide is advantageously used as the metal oxide.

  Butadiene-acrylonitrile rubber and other aliphatic polymers can also be used as plasticizers to improve the toughness of fire protection coatings.

  Examples of reactive diluents that can be used are mono- or polyhydric low molecular weight alcohols that react with epichlorohydrin.

  The epoxy resin used in the fireproof coating of the present invention is generally composed of an epoxy resin component and a curing agent component.

  Bisphenol A, bisphenol F or mixtures thereof are preferred as the epoxy resin component and aliphatic amines are preferred as the hardener component.

  The object of the present invention is likewise to react a epoxy resin and a flame retardant mixture in a process for producing a fire-resistant paint comprising an epoxy resin and a flame retardant mixture as described above and then convert it to a fire-resistant paint with a curing agent. Characterized by the above method.

  In this method, a solvent and a diluent may be used in some cases. An aprotic polar solvent is advantageous in this case. Examples thereof include N-methylpyrrolidone, dimethylformamide, ethers such as diethyl ether, tetrahydrofuran, dioxane, ethyl glycol ethers having a linear or branched alkyl group having 1 to 6 carbon atoms, propylene glycol ethers. And butyl glycol ethers.

  Examples of other solvents that can be used are ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and the like, and ethers such as ethyl acetate, butyl acetate, ethylene glycol acetate and methoxypropyl acetate. Other suitable solvents include halogenated hydrocarbons, and alicyclic and / or aromatic hydrocarbons, with hexane, heptane, cyclohexane, toluene, and dixylenes being preferred. These solvents can be used alone or in a mixed state.

  The reaction with the epoxy resin flame retardant mixture (component A + B) and with the curing agent is preferably carried out at a temperature of −10 to + 150 ° C.

  The present invention also relates to the use of the above fire protection paint. The fire protection paints of the present invention are advantageously used to coat loaded and unloaded metal structures or shapes. The fire-resistant paints of the present invention can also be used to protect floors, walls or molded bodies from stresses due to temperature.

  The fire protection paint of the present invention has good flame retardancy and can be easily processed. This method is advantageous for mixing the epoxy resin and the curing agent component or each component containing them immediately before application. In another advantageous method, the system containing the epoxy resin and the system containing the hardener component are heated slightly to reduce the viscosity. This is preferably simple to spray coat by the airless method. In general, these systems to be heated should be heated to 50-75 ° C. and the temperature of the system to be heated should preferably be between 65 ° C. and 70 ° C. just prior to application.

  In the following examples, a foam fire protection paint is produced and tested for its performance. The heat insulating ability of the foam fireproof paint was tested with a small test ring in the same manner as DIN 4102 Chapter 8 (1986) and using a heating curve as in ISO 834 (1975). Thermal gravimetric analysis evaluation of the flame retardant mixture was carried out by analytical method using “NETZSCH STA 409C” thermobalance.

Examples 1-5:
The following products were used in the following examples.

^(R) Exolit AP422 (Clariant GmbH):
^(R) Exolit AP422 is a free-flowing powdery polyphosphate ammonium polyphosphate represented by the formula (NH ₄ PO ₃ ) _n (n = 20 to 1000, particularly 200 to 1000). .
^(R) Exolit AP750 (Clariant GmbH): a halogen-free flame retardant mixture containing the polymeric ammonium polyphosphate as a synergist with an aromatic carboxylic acid ester of tris (2-hydroxyethyl) -isocyanate.
^(R) Exolit OP1230 (Clariant GmbH): ^(R) Exolit OP1230 is a fine, non-hygroscopic powder based on organic phosphinates and insoluble in water and insoluble in conventional organic solvents.
^(R) Beckopox EP140 (UCB-Surface Specialties): This is a low molecular condensate consisting of bisphenol A and epichlorohydrin having a density of 1.16 g / mL (25 ° C.) and an epoxy equivalent of 180-190. .
^(R) Beckopox EH624 (UCB-Surface Specialties): This has an active H equivalent of 80 g / mol and 2300-3800 mPa.s. It is an aliphatic polyamine having a kinematic viscosity of s (23 ° C.).
^{Tronox (R) R-KB-} 5 (Kerr Mc-Gee Chemical LLC): this is the processed and then the surface rutile titanium dioxide has been stabilized with Al ₂ O ₃ in Al component and Zr components.
Optibor ^(R) borate (Deutsche Borax GmbH): This is a pure boric acid of the formula (H ₃ BO _3).

Example 1 (comparative example):
100 parts Beckopox EP 140, 25 parts boric acid, 2 parts TiO ₂ , and 100 parts Exolit AP422 were introduced back and forth into a stirred vessel and reacted well with 43 parts Beckopox EH 624 after thorough mixing. Let The fireproof paint obtained is applied to one side of a steel plate (St37) with dimensions of 280 × 280 × 6 mm using a roller. The coating is cured at room temperature for 1 day and the layer thickness is 3.5 mm. The surface of the coating is smooth and free of cracks.

  The coated board exhibits a fire resistance of 33 minutes in a flame resistance test according to DIN 4102. The reaction starts at T = 240 ° C.

Example 2 (comparative example):
The fire protection paint used was the same as that used in Example 1, but Exolit AP750 was used instead of Exolit AP422. The fireproof paint obtained is applied to one side of a steel plate (St37) with dimensions of 280 × 280 × 6 mm using a roller. The coating is cured at room temperature for 1 day and the layer thickness is 3.5 mm.

  The surface of the coating is smooth and free of cracks.

  The painted board exhibits a fire resistance of 41 minutes in a flame resistance test according to DIN 4102. The reaction starts at T = 220 ° C.

Example 3 (Example):
A stirred vessel containing 5 parts of a heterogeneous flame retardant mixture consisting of 100 parts Beckopox EP 140, 25 parts boric acid, 9 parts tris (hydroxyethyl) isocyanurate, 2 parts TiO ₂ and Exolit AP422 and Exolit OP1230 Introduced back and forth in, and after thorough mixing, is reacted with 43 parts of Beckopox EH 624. The fireproof paint obtained is applied to one side of a steel plate (St37) with dimensions of 280 × 280 × 6 mm using a roller. The coating is cured at room temperature for 1 day and the layer thickness is 3.5 mm.

  The surface of the coating is smooth and free of cracks.

  The coated board exhibits a fire resistance of 44 minutes in a flame test according to DIN 4102. The reaction starts at T = 179 ° C.

Example 4 (Example):
100 parts Beckopox EP 140, 25 parts boric acid, 9 parts tris (hydroxyethyl) isocyanurate, 2 parts TiO ₂ , and 60 parts heterogeneous flame retardant mixture of Exolit AP422 and Exolit OP1230 Introduced back and forth in, and after thorough mixing, is reacted with 43 parts of Beckopox EH 624. The fireproof paint obtained is applied to one side of a steel plate (St37) with dimensions of 280 × 280 × 6 mm using a roller. The coating is cured at room temperature for 1 day and the layer thickness is 3.5 mm.

  The surface of the coating is smooth and free of cracks.

  The painted board exhibits a fire resistance of 49 minutes in a flame resistance test according to DIN 4102. The reaction starts at T = 175 ° C.

Example 5 (Example):
A stirred vessel containing 100 parts of Beckopox EP 140, 25 parts boric acid, 9 parts tris (hydroxyethyl) isocyanurate, 2 parts TiO ₂ , and 140 parts heterogeneous flame retardant mixture of Exolit AP422 and Exolit OP1230 Introduced back and forth in, and after thorough mixing, is reacted with 43 parts of Beckopox EH 624. The fireproof paint obtained is applied to one side of a steel plate (St37) with dimensions of 280 × 280 × 6 mm using a roller. The coating is cured at room temperature for 1 day and the layer thickness is 3.5 mm.

  The surface of the coating is smooth and free of cracks.

  The coated board exhibits a fire resistance of 59 minutes in a flame resistance test according to DIN 4102. The reaction starts at T = 164 ° C.

Example 6 (Example):
The fire protection paint produced is the same as that produced in Example 5, but the coating thickness is 2.0 mm. The surface of the coating is smooth and free of cracks.

  The painted board exhibits a fire resistance of 42 minutes in a flame resistance test according to DIN 4102. The reaction starts at T = 166 ° C.

Example 7 (Example):
The flame retardant mixture from Examples 3 and 4 and the individual components Exolit AP422 and Exolit OP1230 contained therein are compared by thermogravimetric analysis. The fact that the reaction of the flame retardant mixture starts significantly earlier demonstrates a synergistic effect compared to the case of using the individual components (see FIG. 1).

FIG. 1 is a graph showing the results of thermogravimetric analysis of Example 7.

Claims (15)

A fire-resistant paint for forming a heat-insulating layer contains a phosphorus-based / nitrogen-based flame retardant, a phosphinate represented by the following formula (I) and / or a diphosphinate of the following formula (II) and / or a polymer thereof: The above fire-resistant paint containing a flame retardant mixture.
[Where:
R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ alkyl and / or aryl;
R ³ represents linear or branched C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, C ₆ -C _10-
Alkylarylene, or C ₆ -C ₁₀ -arylalkylene,
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;
m is 1 to 4,
n is 1 to 4,
x is 1-4] The phosphorus-based / nitrogen-based flame retardant is a nitrogen-containing phosphate represented by the formula (NH ₄ ) _y H _3-y PO ₄ or (NH ₄ PO ₃ ) _z , where y is 1 to 3. And the fire-proof coating material which forms the heat insulation layer of Claim 1 whose z is 1-1000. The fire-resistant paint for forming a heat insulating layer according to claim 1 or 2, wherein the phosphorus-based / nitrogen-based flame retardant is ammonium hydrogen phosphate, ammonium dihydrogen phosphate and / or ammonium polyphosphate. The phosphorus-based / nitrogen-based flame retardant is an ammonium polyphosphate represented by the formula (NH ₄ PO ₃ ) _n , wherein n is 10 to ≦ 1000, preferably 200 to ≦ 1000. A fire-proof paint that forms the heat-insulating layer according to any one of the above. Phosphorus / nitrogen flame retardant is a reaction product of melamine and phosphoric acid or condensed phosphoric acid, or a reaction product of melamine condensation product and phosphoric acid or condensed phosphoric acid or products thereof The fire-proof paint which forms the heat insulation layer of Claim 1 which is a mixture of these. Phosphorus / nitrogen flame retardants are melam, melem, or melon, dimelamine phosphate, dimelamine pyrophosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, and melon polyphosphate 6. A fire-proof paint for forming a heat-insulating layer according to claim 5, which is / or melem polyphosphate or a mixed poly salt of these kinds. Containing a phosphorus / nitrogen flame retardant, containing a phosphinate of formula (I) and / or containing a diphosphinate of formula (II) and / or converting these polymers to 0.1-100 (phosphorus System / nitrogen-based flame retardant): The fire-proof paint which forms the heat insulation layer as described in any one of Claims 1-6 contained by the weight ratio of 100-0.1 (phosphinate). Containing a phosphorus-based / nitrogen-based flame retardant, containing a phosphinate of formula (I) and / or containing a diphosphinate of formula (II) and / or converting these polymers to 1-50 (phosphorus / The fireproof coating material which forms the heat insulation layer as described in any one of Claims 1-7 contained by the weight ratio of nitrogen-type flame retardant): 50-1 (phosphinic acid salt). A) 1 to 99% by weight of epoxy resin and B) 1 to 99% by weight of phosphorus / nitrogen flame retardant and phosphinate of formula (I) and / or diphosphinate of formula (II) and / or Flame retardant mixtures containing these polymers,
C) The fire-proof paint which forms the heat insulation layer as described in any one of Claims 1-8 containing the other additive of 0 to 60 weight%. A) 10 to 90% by weight of epoxy resin and B) 2 to 60% by weight of phosphorus / nitrogen flame retardant and phosphinate of formula (I) and / or diphosphinate of formula (II) and / or Flame retardant mixtures containing these polymers,
C) The fire-proof paint which forms the heat insulation layer as described in any one of Claims 1-9 containing the other additive of 3 to 45 weight%. A) 30-85% by weight of epoxy resin and B) 3-50% by weight of phosphorus / nitrogen flame retardant and phosphinate of formula (I) and / or diphosphinate of formula (II) and / or Flame retardant mixtures containing these polymers,
C) The fire-proof paint which forms the heat insulation layer as described in any one of Claims 1-10 containing the other additive of 5 to 40 weight%. 0-60% by weight of additives such as accelerators, fillers, auxiliaries, swelling agents, nitrogenous synergists, carbon donors, pigments, plasticizers and / or reactive diluents and possibly other The fire-resistant coating material which forms the heat insulation layer as described in any one of Claims 1-11 containing an additive. The fireproof coating material which forms the heat insulation layer as described in any one of Claims 1-12 whose M is calcium, aluminum, or zinc. R ¹ and R ² are identical or different and are methyl, ethyl, n- propyl, isopropyl, n- butyl, tert - butyl, n- pentyl and / or phenyl, any one of claims 1 to 13 Fire protection paint that forms two thermal barrier layers. R ³ is methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene; phenylene or naphthylene; methylphenylene, ethylphenylene, tert-butyl. The fire-proof paint which forms a heat insulation layer as described in any one of Claims 1-13 which is phenylene, methyl naphthylene, ethyl naphthylene, or tertiary- butyl naphthylene; Phenyl methylene, phenyl ethylene, phenyl propylene, or phenyl butylene.